CN103409098A - Lignin modified cationic waterborne polyurethane (WPU) adhesive and preparation method thereof - Google Patents
Lignin modified cationic waterborne polyurethane (WPU) adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention provides a lignin modified cationic waterborne polyurethane (WPU) adhesive and a preparation method thereof, and belongs to the field of WPU adhesives and the lignin modified cationic WPU adhesive can be used for solving the problem that existing lignin modified WPU adhesives have poor adhesion. The adhesive comprises the following components in parts by weight: 100 parts of lignin modified cationic WPU, 0.015-0.032 parts of waterborne thickening agent, 0.018-0.026 parts of waterborne leveling agent, 8-16 parts of plasticizer and 5-9 parts of waterborne curing agent. The lignin modified cationic WPU adhesive has the beneficial effects that the lignin structure is introduced into a main polymer chain structure through polymerization reaction between phenolic hydroxy in lignin and polyisocyanate; the adhesion of the cationic waterborne adhesive is improved. The invention also provides the preparation method of the lignin modified cationic WPU adhesive. The shear strength of the adhesive can reach 2.83MPa and the tensile strength can reach 15.5MPa.
Description
Technical field
The invention belongs to the water-based polyurethane adhesive field, be specifically related to lignin modification cation aqueous polyurethane tackiness agent and preparation method thereof.
Background technology
Xylogen is that the content of occurring in nature is only second to cellulosic second largest renewable resources, and industrial lignin is the Main By product of pulp industry, and only paper industry every year will be from isolating the xylogen of 5,000 ten thousand tons plant.Up to now, the xylogen over 95% still directly enters in rivers with " black liquor ", and environment has been caused to severe contamination, therefore, effectively utilizes xylogen extremely important.
Aqueous polyurethane is a kind of polymer that can be dispersed in water, and is a kind ofly to take the macromolecular material of water as dispersion medium by what vulcabond, polymer diatomic alcohol, wetting ability dibasic alcohol, small molecules dibasic alcohol or diamine chain extension formed.At present, be widely applied to tackiness agent, coating, hide finishes, fabric-treating agent etc., wherein at adhesive area, be most widely used.Patent CN100478375C has reported a kind of preparation method of lignin modified water polyurethane, at first polyisocyanates is reacted and obtains the aqueous polyurethane prepolymer at 50-90 ℃ of lower stirring reaction 1-5 hour with polyether glycol or polyester polyol; Then, add the multiple functional radical small molecule chain extender stirring reaction that contains hydrophilic radical to carry out chain extension and crosslinked in 1-3 hour; Finally, add neutralizing agent to neutralize, the adjusting pH value is 6-8, in and after 5-10 minute, be cooled to below 40 ℃ again to disperse with frozen water and xylogen (total amount 1.5%), obtain aqueous polyurethane, this aqueous polyurethane is anion aqueous polyurethane.Before the modification relative to tensile strength of the elongation at break of the lignin modified water polyurethane that this invention obtains, all be significantly improved, simultaneously its low production cost and have characteristics biodegradable, environmental protection.
Yet, the xylogen of reporting in above-mentioned patent is sulfonated lignin, after small molecule chain extender is to the base polyurethane prepolymer for use as chain extension, add, thereby xylogen does not participate in chemical reaction, do not become a segment in the polyurethane backbone structure, it is only the physical blending of sulfonated lignin and aqueous polyurethane, thereby the adhesive property of the aqueous polyurethane obtained is undesirable, await further raising.
Summary of the invention
The objective of the invention is the problem for the bad adhesion that solves existing lignin modified water polyurethane tackiness agent, and lignin modification cation aqueous polyurethane tackiness agent and preparation method thereof is provided.
At first the present invention provides a kind of lignin modification cation aqueous polyurethane tackiness agent, and meter comprises following component by weight:
Preferably, described lignin modification cation aqueous polyurethane tackiness agent, meter comprises following component by weight:
Preferably, the preparation method of described lignin modification cation aqueous polyurethane comprises as follows:
Step 1: by polymer diatomic alcohol and TriMethylolPropane(TMP) reaction, then react with polyisocyanates, obtain the first intermediate;
Step 2: the first intermediate that step 1 is obtained with contain amino dihydroxy compound and react, obtain the second intermediate;
Step 3: the second intermediate reaction by xylogen and small molecule chain extender and step 2 obtain obtains the lignin modification cation aqueous polyurethane.
Preferably, described polymer diatomic alcohol is poly adipate succinic acid ester, polypropylene glycol or PCDL.
Preferably, described polyisocyanates is selected from 2,4-tolylene diisocyanate, ditan-4,4 ' a kind of in vulcabond, hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate or dicyclohexyl methane diisocyanate.
It is preferably, described that to contain amino dihydroxy compound be a kind of in N methyldiethanol amine, N-phenyldiethanol-amine or N butyl diethanol amine or N-(3-aminopropyl) diethanolamine.
Preferably, described small molecule chain extender is a kind of in ethylene glycol, BDO, glycol ether or triglycol.
Preferably, described softening agent is a kind of in dibutyl phthalate or dioctyl phthalate (DOP).
Preferably, described waterborne curing agent is a kind of in Bayhydur3100, BayhydurXP2487/1, Bayhydur XP 2547 or Bayhydur XP 2451.
The present invention also provides a kind of preparation method of lignin modification cation aqueous polyurethane tackiness agent, comprises as follows:
In reaction vessel, add lignin modification cation aqueous polyurethane, water-based thickener, water-based flow agent and softening agent, stir 20～30min, and then add waterborne curing agent to stir 1～3min, namely obtain lignin modification cation aqueous polyurethane tackiness agent.
Beneficial effect of the present invention
At first the present invention provides a kind of lignin modification cation aqueous polyurethane tackiness agent, this tackiness agent be take the lignin modification cation aqueous polyurethane and is main component, described lignin modification cation aqueous polyurethane is by the phenolic hydroxyl group in xylogen and the polyreaction of polyisocyanates, lignin structure is incorporated in the main polymer chain structure, due to the use that contains amino dihydroxy compound, greatly strengthened catalytic effect, make this reaction can carry out fully, the adhesiveproperties of having applied fully the excellence of xylogen has improved the cementability of this cation water-based tackiness agent, in addition, because xylogen has replaced the partial polymer dibasic alcohol, thereby, greatly reduce the serious dependence of this water-based polyurethane adhesive to the petrochemical industry resource.Experimental result shows: lignin modification cation aqueous polyurethane tackiness agent shearing resistance of the present invention can reach 2.83MPa, and tensile strength can reach 15.5MPa.
The present invention also provides a kind of preparation method of lignin modification cation aqueous polyurethane tackiness agent, and this preparation method's technique is simple, with low cost, and the lignin modification cation aqueous polyurethane tackiness agent prepared has excellent adhesive property.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these are described is the restriction for further illustrating the features and advantages of the present invention rather than patent of the present invention being required.
At first the present invention provides a kind of lignin modification cation aqueous polyurethane tackiness agent, and meter comprises following component by weight:
100 parts of lignin modification cation aqueous polyurethanes, 0.015～0.032 part of water-based thickener, 0.018～0.026 part of water-based flow agent, 8～16 parts, softening agent, 5～9 parts of waterborne curing agents; Be preferably 100 parts of lignin modification cation aqueous polyurethanes, 0.02～0.028 part of water-based thickener, 0.021～0.025 part of water-based flow agent, 10～14 parts, softening agent, 6～8 parts of waterborne curing agents.
The preparation method of lignin modification cation aqueous polyurethane of the present invention comprises as follows:
Step 1: by polymer diatomic alcohol and TriMethylolPropane(TMP) reaction, then react with polyisocyanates, obtain the first intermediate;
Step 2: the first intermediate that step 1 is obtained with contain amino dihydroxy compound and react, obtain the second intermediate;
Step 3: the second intermediate reaction by xylogen and small molecule chain extender and step 2 obtain obtains the lignin modification cation aqueous polyurethane.
Step 1 is described first reacts polymer diatomic alcohol with TriMethylolPropane(TMP), described temperature of reaction is preferably 110～120 ℃, reaction times is preferably 1～2h, described polymer diatomic alcohol is preferably poly adipate succinic acid ester, polypropylene glycol or PCDL, and more preferably molecular weight is the daltonian poly adipate succinic acid ester of 1000-5000, polypropylene glycol or polycarbonate.
After polymer diatomic alcohol and TriMethylolPropane(TMP) react completely, in reaction vessel, add polyisocyanates, more complete for polyisocyanates is dissolved, in reaction, add solvent, be preferably butanone, described temperature of reaction is preferably 75～85 ℃, and the reaction times is preferably 3.5～5h; Described polyisocyanates is preferably selected from 2,4-tolylene diisocyanate, ditan-4,4 ' a kind of in vulcabond, hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate or dicyclohexyl methane diisocyanate.The mass ratio of described polymer diatomic alcohol, TriMethylolPropane(TMP) and polyisocyanates is (100～500): (13.2～15.8): (71～96).
Step 2 described by the first intermediate with contain amino dihydroxy compound and react, before adding and containing amino dihydroxy compound, first in reaction vessel, add reaction solvent, be preferably butanone, and then dropping contains amino dihydroxy compound, described temperature of reaction is preferably room temperature, reaction times is preferably 0.5～1h, rate of addition is preferably 3～5ml/min, describedly contain amino dihydroxy compound and be preferably N methyldiethanol amine, a kind of in N-phenyldiethanol-amine or N butyl diethanol amine or N-(3-aminopropyl) diethanolamine, contain amino dihydroxy compound as hydrophilic chain extender, in reaction process, play katalysis, make reaction carry out more complete, described polymer diatomic alcohol is (100～500) with the mass ratio that contains amino dihydroxy compound: (6.5～8.9).
Step 3 is described by before xylogen and small molecule chain extender and the second intermediate reaction, first in reaction vessel, add reaction solvent, be preferably butanone, and then add xylogen and small molecule chain extender, described temperature of reaction is preferably 90 ℃, reaction times is preferably 2～3h, described small molecule chain extender is preferably ethylene glycol, 1, a kind of in 4-butyleneglycol, glycol ether or triglycol, the mass ratio of described polymer diatomic alcohol, xylogen and small molecule chain extender is preferably (100～500): (8.6～15.8): (10.6～18.5).After having reacted, in order to remove magazine, in reaction vessel, first add deionized water, then add concentrated hydrochloric acid, after preferably stirring 0.5～1h, the removal of solvent under reduced pressure butanone, namely obtain the lignin modification cation aqueous polyurethane
Water-based thickener of the present invention is preferably the polyurethanes thickening material, and more preferably model is a kind of in ROHM AND HAAS RM-2020 or RM-8W.
It is a kind of in BYK-380N, BYK-381, BYK-307, BYK-341, BYK-345, BYK-346 or BYK-348 that water-based flow agent of the present invention is preferably model that BYK company produces;
Softening agent of the present invention is preferably a kind of in dibutyl phthalate or dioctyl phthalate (DOP);
Waterborne curing agent of the present invention is preferably the water dispersible polyisocyanates, and more preferably the Bayhydur company model of producing is a kind of in Bayhydur3100, Bayhydur XP 2487/1, Bayhydur XP 2547 or Bayhydur XP 2451.
The present invention also provides a kind of preparation method of lignin modification cation aqueous polyurethane tackiness agent, comprise as follows: in reaction vessel, add the lignin modification cation aqueous polyurethane, water-based thickener, water-based flow agent and softening agent, stir 20～30min, be preferably 25～28min, stirring velocity is preferably 1300～1800rpm, 1500～1700rpm more preferably, and then add waterborne curing agent to stir 1～3min, be preferably 1.5～2min, stirring velocity is preferably 2100～2200rpm, 2150～2180rpm more preferably, namely obtain lignin modification cation aqueous polyurethane tackiness agent.
Below in conjunction with specific embodiment, the present invention is done to further detailed description.
Comparative Examples
In there-necked flask, add 1000g poly adipate succinic acid ester (molecular weight 1000 dalton) and 132g TriMethylolPropane(TMP), be warmed up to 110 ℃, reduced pressure 1 hour, and under nitrogen protection, cooled to 85 ℃, the butanone that adds 120ml, drip the 2,4 toluene diisocyanate of 710g, after dropwising, reacted 3.5 hours, and obtained the first intermediate;
Toward the butanone that adds 80ml in the first intermediate, greenhouse cooling, to room temperature, drips the N methyldiethanol amine hydrophilic chain extender of 65g with the speed of 3ml/min, after adding, reacted 0.5 hour, obtains the second intermediate;
Toward the butanone that adds 150ml in the second intermediate, add the ethylene glycol of 106g, be warmed up to 90 ℃, reacted 2 hours, add the 1650ml deionized water, then, add the 86g concentrated hydrochloric acid, to stir 0.5 hour, butanone is removed in decompression, obtains the modified cation aqueous polyurethane.
In 100g modified cation aqueous polyurethane, add 0.015g water-based thickener ROHM AND HAAS RM-2020,0.018g water-based flow agent BYK-380N and the 8g plasticizer phthalic acid dibutylester rotating speed with 1300rpm in high speed agitator to stir 20min; Then add the 5g waterborne curing agent
3100 rotating speeds with 2100rpm stir 1min, obtain the cation aqueous polyurethane tackiness agent.
Embodiment 1
In there-necked flask, add 1000g poly adipate succinic acid ester (molecular weight 1000 dalton) and 132g TriMethylolPropane(TMP), be warmed up to 110 ℃, reduced pressure 1 hour, and under nitrogen protection, cooled to 85 ℃, the butanone that adds 120ml, drip the 2,4 toluene diisocyanate of 710g, after dropwising, reacted 3.5 hours, and obtained the first intermediate;
Toward the butanone that adds 80ml in the first intermediate, greenhouse cooling, to room temperature, drips the N methyldiethanol amine hydrophilic chain extender of 65g with the speed of 3ml/min, after adding, reacted 0.5 hour, obtains the second intermediate;
Toward the butanone that adds 150ml in the second intermediate, add the ethylene glycol of 86g xylogen and 106g, be warmed up to 90 ℃, reacted 2 hours, add the 1650ml deionized water, then, add the 86g concentrated hydrochloric acid, stirred 0.5 hour, butanone is removed in decompression, obtains the lignin modification cation aqueous polyurethane.
Embodiment 2
In there-necked flask, add 5000g poly adipate succinic acid ester (molecular weight is 5000 dalton) and 158g TriMethylolPropane(TMP), be warmed up to 110 ℃, reduced pressure 1 hour, and under nitrogen protection, cooled to 85 ℃, the butanone that adds 180ml, ' vulcabond, after dropwising for the ditan-4,4 of dropping 960g, reacted 5 hours, and obtained the first intermediate;
Toward the butanone that adds 160ml in the first intermediate, greenhouse cooling, to room temperature, drips N-(3-aminopropyl) the diethanolamine hydrophilic chain extender of 89g with the speed of 5ml/min, after adding, reacted 1 hour, obtains the second intermediate;
Toward the butanone that adds 380ml in the second intermediate, add the glycol ether of 158g xylogen and 185g, be warmed up to 90 ℃, reacted 3 hours, add the 2230ml deionized water, then, add the 138g concentrated hydrochloric acid, stirred 1 hour, butanone is removed in decompression, obtains the lignin modification cation aqueous polyurethane.
Embodiment 3
In there-necked flask, add 2000g poly adipate succinic acid ester (molecular weight 2000 dalton) and 146g TriMethylolPropane(TMP), be warmed up to 110 ℃, reduced pressure 1 hour, and under nitrogen protection, cooled to 85 ℃, the butanone that adds 160ml, drip the hexamethylene diisocyanate of 780g, after dropwising, reacted 4 hours, and obtained the first intermediate;
Toward the butanone that adds 120ml in the first intermediate, greenhouse cooling, to room temperature, drips the N methyldiethanol amine hydrophilic chain extender of 71g with the speed of 4ml/min, after adding, reacted 0.5 hour, obtains the second intermediate;
Toward the butanone that adds 200ml in the second intermediate, add the triglycol of 98g xylogen and 132g, be warmed up to 90 ℃, reacted 2.5 hours, add the 1820ml deionized water, then, add the 112g concentrated hydrochloric acid, stirred 1 hour, butanone is removed in decompression, obtains the lignin modification cation aqueous polyurethane.
Embodiment 4
In there-necked flask, add 2800g PCDL (molecular weight 3000 dalton) and 138g TriMethylolPropane(TMP), be warmed up to 110 ℃, reduced pressure 1 hour, under nitrogen protection, cool to 85 ℃, add the butanone of 145ml, drip the isophorone diisocyanate of 850g, after dropwising, reacted 4 hours, obtain the first intermediate;
Toward the butanone that adds 130ml in the first intermediate, greenhouse cooling, to room temperature, drips the N butyl diethanol amine hydrophilic chain extender of 78g with the speed of 3ml/min, after adding, reacted 1 hour, obtains the second intermediate;
Toward the butanone that adds 180ml in the second intermediate, add 1 of 122g xylogen and 135g, the 4-butyleneglycol, be warmed up to 90 ℃, reacted 3 hours, add the 2120ml deionized water, then, add the 102g concentrated hydrochloric acid, stirred 0.5 hour, butanone is removed in decompression, obtains the lignin modification cation aqueous polyurethane.
Embodiment 5
In there-necked flask, add 4850g PCDL (molecular weight 5000 dalton) and 158g TriMethylolPropane(TMP), be warmed up to 110 ℃, reduced pressure 2 hours, under nitrogen protection, cool to 75 ℃, add the butanone of 160ml, drip the dicyclohexyl methane diisocyanate of 910g, after dropwising, reacted 4.5 hours, obtain the first intermediate;
Toward the butanone that adds 150ml in the first intermediate, greenhouse cooling, to room temperature, drips the N-phenyldiethanol-amine hydrophilic chain extender of 80g with the speed of 5ml/min, after adding, reacted 1 hour, obtains the second intermediate;
Toward the butanone that adds 360ml in the second intermediate, add the ethylene glycol of 138g xylogen and 128g, be warmed up to 90 ℃, reacted 2.5 hours, add the 2000ml deionized water, then, add the 108g concentrated hydrochloric acid, stirred 1 hour, butanone is removed in decompression, obtains the lignin modification cation aqueous polyurethane.
Embodiment 6
In there-necked flask, add 1020g polypropylene glycol (molecular weight 1000 dalton) and 132g TriMethylolPropane(TMP), be warmed up to 120 ℃, reduced pressure 1 hour, under nitrogen protection, cool to 80 ℃, add the butanone of 160ml, drip the Methylcyclohexyl diisocyanate of 785g, after dropwising, reacted 5 hours, obtain the first intermediate;
Toward the butanone that adds 120ml in the first intermediate, greenhouse cooling, to room temperature, drips the N methyldiethanol amine hydrophilic chain extender of 79g with the speed of 5ml/min, after adding, reacted 0.5 hour, obtains the second intermediate;
Toward the butanone that adds 230ml in the second intermediate, add the glycol ether of 137g xylogen and 126g, be warmed up to 90 ℃, reacted 2 hours, add the 2230ml deionized water, then, add the 118g concentrated hydrochloric acid, stirred 1 hour, butanone is removed in decompression, obtains the lignin modification cation aqueous polyurethane.
Embodiment 7
In the 100g lignin modification cation aqueous polyurethane obtained toward embodiment 1, add 0.015g water-based thickener ROHM AND HAAS RM-2020,0.018g water-based flow agent BYK-380N and 8g plasticizer phthalic acid dibutylester, the rotating speed with 1300rpm in high speed agitator stirs 20min; Then add 5g waterborne curing agent Bayhydur3100, the rotating speed stirring 1min with 2100rpm, obtain lignin modification cation aqueous polyurethane tackiness agent.
Embodiment 8
In the 100g lignin modification cation aqueous polyurethane obtained toward embodiment 2, add 0.032g water-based thickener RM-8W, 0.026g water-based flow agent BYK-381 and 16g plasticizer phthalic acid dioctyl ester in high speed agitator, stir 30min with the rotating speed of 1800rpm; Then add 9g waterborne curing agent BayhydurXP2487/1, the rotating speed stirring 3min with 2200rpm, obtain lignin modification cation aqueous polyurethane tackiness agent.
Embodiment 9
In the 100g lignin modification cation aqueous polyurethane obtained toward embodiment 3, add 0.025g water-based thickener ROHM AND HAAS RM-2020,0.022g water-based flow agent BYK-345 and 10g plasticizer phthalic acid dioctyl ester in high speed agitator, stir 25min with the rotating speed of 1500rpm; Then add 7g waterborne curing agent BayhydurXP2547, the rotating speed stirring 2min with 2200rpm, obtain lignin modification cation aqueous polyurethane tackiness agent.
Embodiment 10
In the 100g lignin modification cation aqueous polyurethane obtained toward embodiment 4, add 0.022g water-based thickener ROHM AND HAAS RM-8W, 0.021g water-based flow agent BYK-341 and 12g plasticizer phthalic acid dioctyl ester in high speed agitator, stir 26min with the rotating speed of 1600rpm; Then add 8g waterborne curing agent BayhydurXP2451, the rotating speed stirring 3min with 2100rpm, obtain lignin modification cation aqueous polyurethane tackiness agent.
Embodiment 11
In the 100g lignin modification cation aqueous polyurethane obtained toward embodiment 5, add 0.030g water-based thickener ROHM AND HAAS RM-2020,0.023g water-based flow agent BYK-348 and 13g plasticizer phthalic acid dioctyl ester in high speed agitator, stir 30min with the rotating speed of 1400rpm; Then add 8g waterborne curing agent BayhydurXP2547, the rotating speed stirring 2min with 2200rpm, obtain lignin modification cation aqueous polyurethane tackiness agent.
Embodiment 12
In the 100g lignin modification cation aqueous polyurethane obtained toward embodiment 6, add 0.028g water-based thickener ROHM AND HAAS RM-8W, 0.024g water-based flow agent BYK-346 and 13g plasticizer phthalic acid dibutylester in high speed agitator, stir 28min with the rotating speed of 1600rpm; Then add 7g waterborne curing agent Bayhydur3100, the rotating speed stirring 3min with 2100rpm, obtain lignin modification cation aqueous polyurethane tackiness agent.
Will be until bonding base material oil removing, except after steeping, after lignin modification cation aqueous polyurethane tackiness agent spraying prepared by embodiment of the present invention 7-12,60 ℃ place 1min after, will treat that sticky base material is at 75 ℃ of hot pressing 30min, then carry out performance test, test result is as shown in table 1.
Table 1
The explanation of above embodiment is just be used to helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.Multiple modification to these embodiment will be apparent for those skilled in the art, and General Principle as defined herein can be in the situation that do not break away from the spirit or scope of the present invention, realization in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. lignin modification cation aqueous polyurethane tackiness agent, is characterized in that, meter comprises following component by weight:
2. lignin modification cation aqueous polyurethane tackiness agent according to claim 1, is characterized in that, meter comprises following component by weight:
3. according to any one described lignin modification cation aqueous polyurethane tackiness agent of claim 1-2, it is characterized in that the preparation method of described lignin modification cation aqueous polyurethane comprises as follows:
Step 1: by polymer diatomic alcohol and TriMethylolPropane(TMP) reaction, then react with polyisocyanates, obtain the first intermediate;
Step 2: the first intermediate that step 1 is obtained with contain amino dihydroxy compound and react, obtain the second intermediate;
Step 3: the second intermediate reaction by xylogen and small molecule chain extender and step 2 obtain obtains the lignin modification cation aqueous polyurethane.
4. lignin modification cation aqueous polyurethane tackiness agent according to claim 3, is characterized in that, described polymer diatomic alcohol is poly adipate succinic acid ester, polypropylene glycol or PCDL.
5. lignin modification cation aqueous polyurethane tackiness agent according to claim 3, it is characterized in that, described polyisocyanates is selected from 2,4-tolylene diisocyanate, ditan-4,4 ' a kind of in vulcabond, hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate or dicyclohexyl methane diisocyanate.
6. lignin modification cation aqueous polyurethane tackiness agent according to claim 3, it is characterized in that, described to contain amino dihydroxy compound be a kind of in N methyldiethanol amine, N-phenyldiethanol-amine or N butyl diethanol amine or N-(3-aminopropyl) diethanolamine.
7. lignin modification cation aqueous polyurethane tackiness agent according to claim 3, is characterized in that, described small molecule chain extender is a kind of in ethylene glycol, BDO, glycol ether or triglycol.
8. according to any one described lignin modification cation aqueous polyurethane tackiness agent of claim 1-2, it is characterized in that, described softening agent is a kind of in dibutyl phthalate or dioctyl phthalate (DOP).
9. according to any one described lignin modification cation aqueous polyurethane tackiness agent of claim 1-2, it is characterized in that, described waterborne curing agent is a kind of in Bayhydur3100, BayhydurXP2487/1, Bayhydur XP2547 or Bayhydur XP2451.
10. according to the preparation method of any one described lignin modification cation aqueous polyurethane tackiness agent of claim 1-2, it is characterized in that, comprise as follows:
In reaction vessel, add lignin modification cation aqueous polyurethane, water-based thickener, water-based flow agent and softening agent, stir 20～30min, and then add waterborne curing agent to stir 1～3min, namely obtain lignin modification cation aqueous polyurethane tackiness agent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105331325A (en) * | 2015-11-25 | 2016-02-17 | 华南理工大学 | Lignin/polyurethane/polyethyleneimine wood adhesive and preparation method thereof |
| CN110172327A (en) * | 2019-05-31 | 2019-08-27 | 黄敏 | Photocuring composite adhesive and its production technology |
| CN112625652A (en) * | 2020-12-21 | 2021-04-09 | 华南理工大学 | Lignin/polyether polyol supermolecule composite adhesive and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1939950A (en) * | 2006-10-13 | 2007-04-04 | 武汉理工大学 | Production of lignin modified water polyurethane |
| WO2007132617A1 (en) * | 2006-05-15 | 2007-11-22 | Nippon Polyurethane Industry Co., Ltd. | Aqueous modified polyisocyanate, non-yellowing coating composition, and adhesive composition |
| CN101230125A (en) * | 2008-02-29 | 2008-07-30 | 安徽大学 | Water-soluble alcohol-soluble polyurethane and preparation method thereof |
| CN103045150A (en) * | 2013-01-15 | 2013-04-17 | 中国科学院长春应用化学研究所 | Waterborne polyurethane adhesive and preparation method thereof |
-
2013
- 2013-07-15 CN CN201310295555.9A patent/CN103409098B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007132617A1 (en) * | 2006-05-15 | 2007-11-22 | Nippon Polyurethane Industry Co., Ltd. | Aqueous modified polyisocyanate, non-yellowing coating composition, and adhesive composition |
| CN1939950A (en) * | 2006-10-13 | 2007-04-04 | 武汉理工大学 | Production of lignin modified water polyurethane |
| CN101230125A (en) * | 2008-02-29 | 2008-07-30 | 安徽大学 | Water-soluble alcohol-soluble polyurethane and preparation method thereof |
| CN103045150A (en) * | 2013-01-15 | 2013-04-17 | 中国科学院长春应用化学研究所 | Waterborne polyurethane adhesive and preparation method thereof |
Cited By (5)
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| CN105331325A (en) * | 2015-11-25 | 2016-02-17 | 华南理工大学 | Lignin/polyurethane/polyethyleneimine wood adhesive and preparation method thereof |
| CN105331325B (en) * | 2015-11-25 | 2017-12-01 | 华南理工大学 | A kind of lignin/polyurethane/polyethyleneimine based Wood Adhesives and preparation method thereof |
| CN110172327A (en) * | 2019-05-31 | 2019-08-27 | 黄敏 | Photocuring composite adhesive and its production technology |
| CN112625652A (en) * | 2020-12-21 | 2021-04-09 | 华南理工大学 | Lignin/polyether polyol supermolecule composite adhesive and preparation method thereof |
| CN112625652B (en) * | 2020-12-21 | 2021-09-21 | 华南理工大学 | Lignin/polyether polyol supermolecule composite adhesive and preparation method thereof |
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